Hydrophilic elastomers for microcontact printing of polar inks

A moderately hydrophilic, thermoplastic elastomer (poly(ether-ester)) was investigated as a stamp material for microcontact printing of a polar ink: pentaerythritol-tetrakis-(3-mercaptopropionate). Stamps with a relief structure were produced from this polymer by hot embossing, and a comparison was made with conventional poly(dimethylsiloxane) (PDMS) and oxygen-plasma-treated PDMS. It is shown that the hydrophilic stamps can be used for the repetitive printing (without re-inking) of at least 10 consecutive patterns, which preserve their etch resistance, and this in rather sharp contrast to conventional and oxygen plasma-treated PDMS stamps. It is argued that these enhanced printing characteristics of the hydrophilic stamps originate from an improved wetting and solubility of polar inks in the hydrophilic stamp.     

Stamping patterns of insulated gold nanowires with self-organized ultrathin polymer films

A thermal contact transfer technique is presented for the fabrication of nanoscaled to microscaled patterns of polymer-insulated metal structures on ceramic surfaces using metal-coated, thermoplastic stamps. The thermally activated formation of polymer-metal-polymer (PMP) heterostructures occurs spontaneously when a metal-coated thermoplastic stamp is compressed against a ceramic substrate and subsequently heated. The presented technique exploits the dynamics of ultrathin polymer films localized at interfaces and interfacial forces to prompt local reorganization of polymer stamp materials during processing. Intercalation of polymer stamp materials into the metal-substrate interface yields a cohesive polymer layer that binds the metal layer to the substrate. Disproportionate adhesion between the bulk polymer and the polymer layer at the stamp-metal interface leaves a capping layer upon separation of the stamp from the substrate. Here we demonstrate this technique with single use, bilevel polymer stamps which afford transfer of two distinct general products. The transfer of insulated submicrometer wide wires from the raised stamp features affords patterns of trilayered PMP structures with uniform wire dimensions. Concomitant transfer from the recessed stamp features allows fabrication of multilayered PMP architectures with sub-100 nm spacing from microstructured polymer stamps. Thus, patterns with two different insulated nanowire widths are readily fabricated in a single stamping process. A variety of ceramic substrates, thermoplastic materials, and metals can be used; e.g., inexpensive gold-coated CD or DVD media can be used as stamps, where the combination of materials dictates the relative interfacial forces and the processing parameters.     

Surface modification of elastomeric stamps for microcontact printing of polar inks

Chemical modification of the surface of a stamp used for microcontact printing (microCP) is interesting for controling the surface properties, such as the hydrophilicity. To print polar inks, plasma polymerization of allylamine (PPAA) was employed to render the surface of poly(dimethylsiloxane) (PDMS), polyolefin plastomers (POP), and Kraton elatomeric stamps hydrophilic for long periods of time. A thin PPAA film of about 5 nm was deposited on the stamps, which increased the hydrophilicity, and which remained stable for at least several months. These surface-modified stamps were used to transfer polar inks by microCP. The employed microCP schemes are as follows: (a) a second generation of dendritic ink having eight dialkyl sulfide end groups to fabricate patterns on gold substrates by positive microCP, (b) fluorescent guest molecules on beta-cyclodextrin (beta-CD) printboards on glass employing host-guest recognition, and (c) Lucifer Yellow ethylenediamine resulting in covalent patterning on an aldehyde-terminated glass surface. All experiments resulted in an excellent performance of all three PPAA-coated stamp materials to transfer the polar inks from the stamp surface to gold and glass substrates by microCP, even from aqueous solutions.     

Effect of stamp deformation on the quality of microcontact printing: theory and experiment

Microcontact printing (microCP) is an effective way to generate micrometer- or submicrometer-sized patterns on a variety of substrates. However, the fidelity of the final pattern depends critically on the coupled phenomena of stamp deformation, fluid transfer between surfaces, and the ability of the ink to self-assemble on the substrate. In particular, stamp deformation can produce undesirable effects that limit the practice and precision of microCP. Experimental observations and comparison with theoretical predictions are presented here for three of the most undesirable consequences of stamp deformation: (1) roof collapse of low aspect ratio recesses, (2) buckling of high aspect ratio plates, and (3) lateral sticking of high aspect ratio plates. Stamp behavior was observed visually with an inverted optical microscope while load-displacement data were collected during compression and retraction of stamps. Additionally, a "robotic stamper" was used to deliver ink patterns in precise locations on substrates. These monomolecular ink patterns were then observed in high contrast using the surface potential scanning mode of an atomic force microscope. Theoretical models based on continuum mechanics were used to accurately predict both physical deformation of the stamp and the resultant inking patterns. The close agreement between these models and the experimental data presented clearly demonstrates the essential considerations one must weigh when designing stamp geometry, material, and loading conditions for optimal pattern fidelity.     

Microscale features and surface chemical functionality patterned by electron beam lithography: a novel route to poly(dimethylsiloxane) (PDMS) stamp fabrication

Poly(dimethylsiloxane) (PDMS) has become a ubiquitous material for microcontact printing, yet there are few methods available to pattern a completed PDMS stamp in a single step. It is shown here that electron beam lithography (EBL) is effective in writing patterns directly onto cured PDMS stamps, thus overcoming the need for multiple patterning steps. Not only does this method allow the modification of an existing lithographic pattern, but new 3D features such as cones, pits, and channels can also be fabricated. EBL can also be used to fabricate PDMS masks for photolithography whereby 1:1 pattern transfer into a photoresist is achieved. Additionally, direct EBL writing of surface chemical features has been achieved using a PDMS stamp coated with a self-assembled monolayer. An electrostatic mechanism appears to be operative in the EBL patterning process, as supported by calculations, thermogravimetric analysis, time-of-flight secondary ion mass spectroscopy, optical and atomic force microscopy, and chemical functionalization assays.     

A Simple Method for Fabricating Patterned Curvilinear Microstructures in Poly(dimethylsiloxane) by Selective Wetting

The fabrication of patterned microstructures in poly(dimethylsiloxane) (PDMS) is a prerequisite for soft lithography. Herein, curvilinear surface relief microstructures in PDMS are fabricated through a simple three‐stage approach combining microcontact printing (μCP), selective surface wetting/dewetting and replica molding (REM). First, using an original PDMS stamp (first‐generation stamp) with linear relief features, a chemical pattern on gold substrate is generated by μCP using hexadecanethiol (HDT) as an ink. Then, by a dip‐coating process, an ordered polyethylene glycol (PEG) polymer‐dot array forms on the HDT‐patterned gold substrate. Finally, based on a REM process, the PEG‐dot array on gold substrate is used to fabricate a second‐generation PDMS stamp with microcavity array, and the second‐generation PDMS stamp is used to generate third‐generation PDMS stamp with microbump array. These fabricated new‐generation stamps are utilized in μCP and in micromolding in capillaries (MIMIC), allowing the generation of surface micropatterns which cannot be obtained using the original PDMS stamp. The method will be useful in producing new‐generation PDMS stamps, especially for those who want to use soft lithography in their studies but have no access to the microfabrication facilities.     

Chemically patterned flat stamps for microcontact printing

Locally oxidized patterns on flat poly(dimethylsiloxane) stamps for microcontact printing were used as a platform for the transfer of a hydrophilic fluorescent ink to a glass substrate. The contrast was found to be limited. These locally oxidized patterns were conversely used as barriers for the transfer of hydrophobic n-octadecanethiol. In this case a good contrast was obtained, but the pattern was found to be susceptible to defects (cracks) in the barrier layer. Local stamp surface oxidation and subsequent modification with 1H,1H,2H,2H-perfluorodecyltrichlorosilane, for use as a barrier in the transfer of n-octadecanethiol, 16-mercaptohexadecanoic acid, and octanethiol, resulted in remarkably good contrast and stable patterns. The improved ink transfer control is ascribed to the reduction of undesired surface spreading and a superior mechanical stability of the stamp pattern. This new approach substantially expands the applicability of microcontact printing and provides a tool for the faithful reproduction of even extremely low filling ratio patterns.     

Self-supporting hydrogel stamps for the microcontact printing of proteins

In this work we explore a new hydrogel stamp material obtained from polymerizing 2-hydroxyethyl acrylate and poly(ethylene glycol) diacrylate in the presence of water for the microcontact printing of proteins directly on gold substrates and by covalent coupling to self-assembled monolayers of alkanethiols. At high cross-link density, the hydrogel is rigid, hydrophilic, and with a high buffer holding capacity to enable the unsupported printing of protein patterns homogeneously and reproducibly, with micrometer-range precision. The stamps were used to print antibodies to human parathyroid hormone, which were shown using immunoassay tests to retain their biological function with binding capacities comparable to those of solution-adsorbed antibodies.     

Micro/nanopatterning of proteins via contact printing using high aspect ratio PMMA stamps and nanoimprint apparatus

Micro- and nanoscale protein patterns have been produced via a new contact printing method using a nanoimprint lithography apparatus. The main novelty of the technique is the use of poly(methyl methacrylate) (PMMA) instead of the commonly used poly(dimethylsiloxane) (PDMS) stamps. This avoids printing problems due to roof collapse, which limits the usable aspect ratio in microcontact printing to 10:1. The rigidity of the PMMA allows protein patterning using stamps with very high aspect ratios, up to 300 in this case. Conformal contact between the stamp and the substrate is achieved because of the homogeneous pressure applied via the nanoimprint lithography instrument, and it has allowed us to print lines of protein approximately 150 nm wide, at a 400 nm period. This technique, therefore, provides an excellent method for the direct printing of high-density sub-micrometer scale patterns, or, alternatively, micro-/nanopatterns spaced at large distances. The controlled production of these protein patterns is a key factor in biomedical applications such as cell-surface interaction experiments and tissue engineering.     

Versatile Stamps in Microcontact Printing: Transferring Inks by Molecular Recognition and from Ink Reservoirs

Microcontact printing is a heavily used surface modification method in materials and life science applications. This concept article focuses on the development of versatile stamps for microcontact printing that can be used to bind and release inks through molecular recognition or through an ink reservoir, the latter being used for the transfer of heavy inks, such as biomolecules and particles. Conceptually, such stamp properties can be introduced at the stamp surface or by changing the bulk stamp material; both lines of research will be reviewed here. Examples include supramolecular stamps with affinity properties, polymer‐layer‐grafted PDMS stamps, and porous multilayer‐grafted PDMS stamps for the first case, and hydrogel stamps and porous stamps made by phase‐separation micromolding for the second. Potential directions for future advancement of this field are also discussed.     

High-precision microcontact printing of interchangeable stamps using an integrated kinematic coupling

Microcontact printing (μCP) is a rapid, inexpensive way to create microscale chemical or biochemical patterns on a target surface. This microstamping method can be used to selectively modify a wide array of surface properties, from wettability and protein adsorption to chemical etch susceptibility. However, controlling the absolute location of features created with microcontact printing is difficult; this lack of precision makes it challenging to integrate with other microfabrication methods or to create complex, multi-chemical patterns on a single surface. In this research, we demonstrate a novel method of controlling the placement of microcontact printing stamps by using an integrated kinematic coupling device. This technique relies on mechanical reference points for rapid, optics-free registry of the stamp and allows μCP stamps to be quickly removed and replaced or even exchanged with submicron repeatability.     

Printing chemical gradients

We describe a method to exploit the mass-transfer limitations of microcontact printing for the fabrication of surfaces with well-defined, arbitrarily shaped composition variations. An analysis of the transport processes reveals that the printing of hexadecanethiol (HDT) from poly(dimethylsiloxane) is purely diffusion-controlled. Stamps with geometries that enhance surface-normal diffusion paths therefore allow not only the contours, but also the local density of self-assembled monolayers to be controlled. We use stamps with variable thickness and uniform ink concentration to print HDT density gradients on gold, depleting the stamps during the process. In the second step, a perfluorinated thiol fills the vacancies in the partial monolayer to form a two-component gradient that we analyze by means of X-ray photoelectron spectroscopy and spectroscopic ellipsometry. Linear and radial gradients are shown here as examples for a wide range of geometries that can be fabricated with high precision using the method.     

Oxygen plasma-treatment effects on Si transfer

Oxygen plasma-treatment is commonly used to increase the hydrophilicity of poly(dimethylsiloxane) (PDMS) stamps used for microcontact printing (muCP) aqueous-based inks. Review of the literature reveals that a wide range of plasma parameters are currently employed to modify stamp surfaces. However, little is known about the effect of these parameters (e.g., power, chamber pressure, duration) on the undesirable transfer of low-molecular-weight silicon-containing fragments from the stamps that commonly occurs during muCP. To study the effect of oxygen plasma-treatment on Si transfer, unpatterned PDMS stamps were treated with oxygen plasma under various conditions and used to stamp deionized water on plasma-activated poly(methyl methacrylate) (PMMA) substrates. Once stamped, the PMMA substrates were analyzed with X-ray photoelectron spectroscopy (XPS) to quantify and characterize silicon present on the substrate surface. In addition, used PDMS stamps were analyzed with scanning electron microscopy (SEM) to observe topographical changes that occur during oxygen plasma-treatment. XPS results show that all plasma treatments studied significantly reduced the amount of Si transfer from the treated stamps during muCP as compared to untreated PDMS stamps and that the source of transfer is residual PDMS fragments not removed by oxygen plasma. SEM results show that, although the treated stamps undergo a variety of topographical changes, no correlation exists between stamp topography and extent of Si transfer from the stamps.     

Molecular scale modeling of polymer imprint nanolithography

We present the results of large-scale molecular dynamics simulations of two different nanolithographic processes, step-flash imprint lithography (SFIL), and hot embossing. We insert rigid stamps into an entangled bead-spring polymer melt above the glass transition temperature. After equilibration, the polymer is then hardened in one of two ways, depending on the specific process to be modeled. For SFIL, we cross-link the polymer chains by introducing bonds between neighboring beads. To model hot embossing, we instead cool the melt to below the glass transition temperature. We then study the ability of these methods to retain features by removing the stamps, both with a zero-stress removal process in which stamp atoms are instantaneously deleted from the system as well as a more physical process in which the stamp is pulled from the hardened polymer at fixed velocity. We find that it is necessary to coat the stamp with an antifriction coating to achieve clean removal of the stamp. We further find that a high density of cross-links is necessary for good feature retention in the SFIL process. The hot embossing process results in good feature retention at all length scales studied as long as coated, low surface energy stamps are used.     

Microfabrication using elastomeric stamp deformation

Elastomeric stamp deformation has been utilized for the contact printing (CP) of self-assembled monolayers (SAMs) and, more recently, polymers and proteins. Here, we take advantage of this well-studied phenomenon to fabricate a series of new metal thin-film patterns not present on the original stamp. The rounded patterns are of nanoscale thickness, long-range order, and are created from elastomeric stamps with only straight-edged features. The metal was printed onto the surface of an alpha,omega-alkanedithiol self-assembled monolayer (SAM). The new shapes are controlled by a combination of stamp geometry design and the application of external pressure. Previously published rules on stamp deformation for contact printing of SAMs are invalid because the coating is instead a thin-metal film. This method represents a new pathway to micropatterning metal thin films, leading to shapes with higher complexity than the original lithographic masters.     

Microstructuring of p-Si(1 0 0) by localized electrochemical polishing using patterned agarose as a stamp

Localization of electrochemical polishing using patterned agarose has been employed to fabricate microstructures on p-Si(1 0 0). The patterns were first transferred from a master to an agarose stamp, and then the microstructures were fabricated by limiting electrochemical polishing in the small contact area between the stamp and the workpiece. The gel stamp acts as the current flow channel between the working electrode and the counter electrode, simultaneously directing the electrolyte to the preferential parts of the Si workpiece. Microstructures fabricated by partial anodic dissolution on p-Si are approximately the same as those on the master. Lateral deviation of the fabricated microstructures from those on the master is approximately 2.6% and the electrochemical etching rate in HF is around several micrometers in an hour. This newly developed technique can be used as a low-cost and simple approach to fabricate microstructures on p-Si with high fidelity at a fast rate.     

Dendrimer-mediated transfer printing of DNA and RNA microarrays

This paper describes a new method to replicate DNA and RNA microarrays. The technique, which facilitates positioning of DNA and RNA with submicron edge resolution by microcontact printing (muCP), is based on the modification of poly(dimethylsiloxane) (PDMS) stamps with dendrimers ("dendri-stamps"). The modification of PDMS stamps with generation 5 poly(propylene imine) dendrimers (G5-PPI) gives a high density of positive charge on the stamp surface that can attract negatively charged oligonucleotides in a "layer-by-layer" arrangement. DNA as well as RNA is transfer printed from the stamp to a target surface. Imine chemistry is applied to immobilize amino-modified DNA and RNA molecules to an aldehyde-terminated substrate. The labile imine bond is reduced to a stable secondary amine bond, forming a robust connection between the polynucleotide strand and the solid support. Microcontact printed oligonucleotides are distributed homogeneously within the patterned area and available for hybridization. By using a robotic spotting system, an array of hundreds of oligonucleotide spots is deposited on the surface of a flat, dendrimer-modified stamp that is subsequently used for repeated replication of the entire microarray by microcontact printing. The printed microarrays are characterized by homogeneous probe density and regular spot morphology.     

A benchtop method for the fabrication and patterning of nanoscale structures on polymers

A benchtop method for the facile production of nanoscale metal structures on polymers is demonstrated. This approach allows for the design and patterning of a wide range of metallic structures on inexpensive polymer surfaces, affording the fabrication of nanoscaled platforms for use in the design of sensors, actuators, and disposable electronic and photonic devices. Numerous structures, from simple nanowires to multilayered metallic gratings, are demonstrated, with sizes ranging from microns to the nanoscale. The process involves molding a malleable metal film deposited on a rigid substrate such as mica, by the compression of a plastic polymer stamp with the desired pattern against the metal film. While under compression, an etchant is then used to modify the metal. Upon separation of the stamp from the support, micro- to nanoscaled metallic structures are found on the stamp and/or on the substrate. The sizes of the structures formed depend on the sizes of the features on the stamp but can be fine-tuned by about 4-fold through variations in both pressure and duration of etching. Also, depending on the processing, multiple dimension metallic structures can be obtained simultaneously in a single stamping procedure. The metallic structures formed on the stamp can also be subsequently transferred to another surface allowing for the construction of multilayered materials such as band gap gratings or the application of electrical contacts. Using this approach, fabrication of both simple and complex micro- to nanoscaled structures can be accomplished by most any researcher as even the grating structure of commercial compact disks may be used as stamps, eliminating the requirement of expensive lithographic processes to form simple structures.     

Millimeter-scale contact printing of aqueous solutions using a stamp made out of paper and tape

This communication describes a simple method for printing aqueous solutions with millimeter-scale patterns on a variety of substrates using an easily fabricated, paper-based microfluidic device (a paper-based "stamp") as a contact printing device. The device is made from inexpensive materials, and it is easily assembled by hand; this method is thus accessible to a wide range of laboratories and budgets. A single device was used to print over 2500 spots in less than three minutes at a density of 16 spots per square centimetre. This method provides a new tool to pattern biochemicals-reagents, antigens, proteins, and DNA-on planar substrates. The accuracy of the volume of fluid delivered in simple paper-to-paper printing is low, and although the pattern transfer is rapid, it is better suited for qualitative than accurate, quantitative work. By patterning the paper to which the transfer occurs using wax printing or an equivalent technique, accuracy increases substantially.     

Reactive microCP on ultrathin block copolymer films: investigation of the microCP mechanism and application to sub-microm (bio)molecular patterning

In this paper, the mechanism of the recently introduced soft lithographic patterning approach of reactive microcontact printing on thin substrate-supported polystyrene-block-poly(tert-butyl acrylate) (PS690-b-PtBA1210) films using trifluoroacetic acid (TFA)-inked elastomeric poly(dimethylsiloxane) (PDMS) stamps is investigated in detail. In this approach, solventless deprotection reactions are carried out with very high spatial definition using TFA as a volatile reagent that partitions into the PtBA skin layer. On the basis of a systematic investigation of the process, ink loading was identified as a crucial parameter for obtaining faithful pattern transfer. Using optimized conditions, submicrometer-sized patterns were successfully fabricated. In combination with subsequent wet chemical covalent coupling of various (bio)molecules, reactive microCP is established as an approach to afford positive, as well as negative, images of the features of the stamps used. In addition, the size of the patterned areas was manipulated by exploiting the controlled spreading of the ink; thus, stamps with identical features yield patterns with different sizes, yet identical periodicity, as shown for bovine serum albumin (BSA)-poly(ethylene glycol) patterns. The reactive microCP methodology affords new pathways for submicrometer-scale patterning of bioreactive surfaces.